Claims:

1. A method for depositing a metal containing film on to one or more
substrates, comprising:a) providing at least one substrate into a
reactor;b) introducing at least one metal containing precursor into the
reactor,wherein the metal containing precursor has the general formula:
##STR00005## and wherein: M is a metal selected from one of copper,
silver and gold; R, R', R'' are independently selected from: H; a C1-C6
linear, branched, or cyclic alkyl group; NO2; SiR1R2R3;
and GeR1R2R3; R1, R2, R3 are independently
selected from: H; and a C1-C6 linear, branched or cyclic alkyl group; and
L is a neutral ligand derivated from ethylene or acetylene; andc)
depositing at least part of the metal containing precursor to form a
metal containing film, pure metal or alloy, on the one or more
substrates.

2. The method of claim 1, further comprising depositing the metal
containing film onto the at least one substrate at a temperature between
about 70.degree. C. and about 450.degree. C.

3. The method of claim 2, further comprising depositing the metal
containing film onto the at least one substrate at a temperature between
about 70.degree. C. and about 200.degree. C.

6. The method of claim 5, wherein the second precursor comprises at least
one member selected from the group consisting of: Ag, Au, Cu, Ru, and Ta.

7. The method of claim 1, further comprising:a) providing at least one
inert fluid and a reaction fluid into said reactor, wherein said reaction
fluid is a hydrogen containing or a reducing fluid; andb) reacting said
metal containing precursor with said reaction fluid.

9. The method of claim 7, wherein the reaction fluid is a reducing fluid
selected from CO and Si2Cl.sub.6.

10. The method of claim 1, wherein the pressure in the reactor is between
about 1 Pa and about 100,000 Pa.

11. The method of claim 10, wherein the pressure is between about 25 Pa
and about 1000 Pa.

12. The method of claim 1, wherein the metal containing precursor, the
inert fluid, and the reaction fluid are either introduced at least
partially simultaneously as in a chemical vapor deposition process, or
are introduced at least partially sequentially as in an atomic layer
deposition process.

13. The method of claim 1, further comprising introducing at least one
metal containing precursor into the reactor, wherein the metal containing
precursor has a melting point of less than about 50.degree. C.

14. The method of claim 13, wherein the metal containing precursor has a
melting point of less than about 35.degree. C.

15. The method of claim 12, wherein the metal containing precursor is a
liquid at room temperature.

17. A method for depositing a metal containing film on to one or more
substrates with a PEALD process, comprising:a) providing at least one
substrate into a reactor;b) introducing at least one metal containing
precursor into the reactor,wherein the metal containing precursor has the
general formula: ##STR00006## and wherein: M is a metal selected from one
of copper, silver and gold; R, R', R'' are independently selected from:
H; a C1-C6 linear, branched, or cyclic alkyl group; NO2;
SiR1R2R3; and GeR1R2R3; R1, R2,
R3 are independently selected from: H; and a C1-C6 linear, branched
or cyclic alkyl group; and L is a neutral ligand derivated from ethylene
or acetylene;c) providing at least one inert fluid and a reaction fluid
into said reactor, wherein said reaction fluid is a hydrogen containing
or a reducing fluid;d) providing a plasma source, and sequentially
activating and deactivating the plasma source after the introduction of
the metal containing precursor;e) reacting the metal containing precursor
with the reaction fluid; andf) depositing at least part of the metal
containing precursor to form a metal containing film, pure metal or
alloy, on the one or more substrates.

18. The method of claim 17, wherein steps (b) through (f) are repeated
until a desired thickness of film is obtained.

19. The method of claim 17, wherein L is bis(trimethylsilyl)acetylene.

20. The method of claim 17, further comprising depositing the metal
containing film onto the at least one substrate at a temperature between
about 200.degree. C. and about 50.degree. C.

21. The method of claim 21, further comprising depositing the metal
containing film onto the at least one substrate at a temperature between
about 150.degree. C. and about 50.degree. C.

23. The method of claim 17, wherein the reaction fluid is a reducing fluid
selected from CO and Si2Cl.sub.6.

24. The method of claim 17, wherein the pressure in the reactor is between
about 1 Pa and about 100,000 Pa.

25. The method of claim 24, wherein the pressure is between about 25 Pa
and about 1000 Pa.

26. The method of claim 17, further comprising introducing at least one
metal containing precursor into the reactor, wherein the metal containing
precursor has a melting point of less than about 50.degree. C.

27. The method of claim 26, wherein the metal containing precursor has a
melting point of less than about 35.degree. C.

28. The method of claim 26, wherein the metal containing precursor is a
liquid at room temperature.

31. The method of claim 30, wherein the second precursor comprises at
least one member selected from the group consisting of: Ag, Au, Cu, Ru,
and Ta.

32. A new composition comprising a precursor with the general formula:
##STR00007## wherein:M is a metal selected from one of copper, silver and
gold;R, R', R'' are independently selected from: H; a C1-C6 linear,
branched, or cyclic alkyl group; NO2; SiR1R2R3; and
GeR1R2R3;R1, R2, R3 are independently
selected from: H; and a C1-C6 linear, branched or cyclic alkyl group;L is
a neutral ligand derivated from ethylene or acetylene; andthe precursor
has a melting point lower than about 50.degree. C.

33. The composition of claim 32, wherein L is
bis(trimethylsilyl)acetylene.

[0003]This invention relates generally the deposition of thin films, as
used in the manufacture of semiconductor, photovoltaic or TFT-LCD
devices. More specifically, the invention relates to compositions and
methods for depositing a copper, silver or gold containing precursors.

[0004]2. Background of the Invention

[0005]ALD (Atomic Layer Deposition) and CVD (Chemical Vapor Deposition)
are particularly useful techniques for deposition of metal films as
compared to other methods of deposition such as physical vapor deposition
(PVD) methods like sputtering, molecular beam epitaxy, and ion beam
implantation. ALD and CVD can also be used to provide flexibility in the
design of manufacturing electronic devices including the potential to
reduce the number of processing phases required to provide a desired
product. These techniques allow conformal deposition, selective
deposition for the deposition of copper, silver, gold and other
materials. Suitable processes to form metal films require the
identification of relevant precursors requiring strict requirements such
as being thermally stable, easily vaporized, reactive, with clean
decomposition.

[0006]The need for high performance interconnection materials increases as
device feature sizes shrink and device density increases. Copper provides
an alternative to CVD of aluminum in ultra large scale integrated (ULSI)
devices due to its low resistivity (1.67 μΩcm for Cu, 2.65
μΩcm for Al), high electromigration resistance and high melting
point (1083° C. for Cu, 660° C. for Al). Its low
interconnect resistivity also may allow for faster devices.

[0007]Copper precursors are quite volatile and show low deposition
temperatures, but are highly, sensitive to heat and oxygen. The latter
precursors are rather stable, but are isolated as solids with high
melting points and thus require high deposition temperatures. It is
common for impurities such as carbon or oxygen to be incorporated during
the thermal CVD process when using certain organometallic precursors. For
instance, (η5-C 5H 5)Cu(PMe3) produces copper films leading to
incorporation of phosphorus. Moreover, phosphine-containing molecules are
disqualified because of their high toxicity. Organic phosphines are very
hazardous and PF3 being both hazardous and might lead to undesired
phosphorus contamination and fluorine-induced etching/damage. Such
chemicals might therefore be subject to strict regulations.

[0008]An example of an existing copper precursor includes
(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate)CuL ((hfac)CuL), where L is a
Lewis base. These types of precursors have been the most studied copper
precursors to date because they can deposit copper via a thermal
disproportionation reaction. Especially
(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate)Cu(trimethylvinylsilane),
which has attracted much attention because it is a liquid with reasonably
high vapor pressure. Other copper compounds such as
(1,1,1,5,5,5-hexafluoro-2,4-pentanedionate)CuL, where L is
1,5-cyclooctadiene (CUD), alkyne or trialkylphosphine, are either solids
or liquids with a low vapor pressure. Although
(hfac)Cu(trimethylvinylsilane) ((hfac)Cu(tmvs)) has been the most
utilized copper precursor, its stability is not satisfactory for the
selective growth of copper films with reproducibility. In addition,
studies have demonstrated that the chemical vapor deposition reaction of
(hfac)Cu(tmvs) under ultra high vacuum conditions produced contamination
by carbon and fluorine in the deposited films. Therefore, a precursor
with high volatility and stability, which contains no fluorinated
ligands, is more desirable for the deposition of copper by CVD.

[0009]Copper compounds of acetoacetate derivatives which contain no
fluorinated ligands have been previously used as CVD precursors. Although
these compounds were reported to be volatile and capable of depositing
copper films at low substrate temperatures. The studied acetoacetate
derivatives were found to be attractive since they were volatile without
employing fluorinated ligands and deposited copper films at temperatures
below 200° C. However, these derivatives are solid with high
melting points and are incapable of selective deposition of copper. On
the other hand, the Cu(I) acetoacetate derivatives deposited copper films
at relatively low temperatures via disproportionation reaction. However,
few are practical for use as CVD precursors since they are either solids
or liquids with a low vapor pressure or they have an extremely low
thermal stability (i.e. their decomposition temperature is within a few
degrees of their vaporization temperature).

[0010]Consequently, there exists a need for alternate precursors for
deposition of copper, silver, or gold containing films.

[0012]In an embodiment, a method for depositing a metal containing film
onto one or more substrates comprises providing at least one substrate
into a reactor. At least one metal containing precursor is introduced
into the reactor, wherein the metal containing precursor has the general
formula:

##STR00001##

[0013]M is one of copper, silver or gold. R, R', and R'' are selected from
hydrogen, a C1-C6 linear, branched or cyclic alkyl group, NO2,
SiR1R2R3; and GeR1R2R3. R1, R2,
R3 are independently selected from hydrogen, and a C1-C6 linear,
branched or cyclic alkyl group. L is a neutral ligand derivated from
ethylene or acetylene. At least part of the metal containing precursor is
deposited onto one or more of the substrates to form either a pure metal
film, or an alloy film.

[0014]In another embodiment, a method for depositing a metal containing
film onto one or more substrates comprises providing at least one
substrate into a reactor. At least one metal containing precursor is
introduced into the reactor, wherein the metal containing precursor has
the general formula:

##STR00002##

[0015]M is one of copper, silver or gold. R, R', and R'' are selected from
hydrogen, a C1-C6 linear, branched or cyclic alkyl group, NO2,
SiR1R2R3; and GeR1R2R3. R1, R2,
R3 are independently selected from hydrogen, and a C1-C6 linear,
branched or cyclic alkyl group. L is a neutral ligand derivated from
ethylene or acetylene. A plasma source is provided, and sequentially
activated/deactivated after the introduction of the metal containing
precursor. At least part of the metal containing precursor is deposited
onto one or more of the substrates to form either a pure metal film, or
an alloy film.

[0016]In another embodiment, a composition comprises a precursor with the
general formula:

##STR00003##

[0017]M is one of copper, silver or gold. R, R', and R'' are selected from
hydrogen, a C1-C6 linear, branched or cyclic alkyl group, NO2,
SiR1R2R3; and GeR1R2R3. R1, R2,
R3 are independently selected from hydrogen, and a C1-C6 linear,
branched or cyclic alkyl group. L is a neutral ligand derivated from
ethylene or acetylene.

[0018]Other embodiments of the current invention may include, with out
limitation, one or more of the following features: [0019]L is
bis(trimethylsilyl)acetylene; [0020]the metal containing film is
deposited onto at least one substrate at a temperature between about
70° C. and about 450° C.; preferably between about
70° C. and about 200° C.; [0021]the metal containing film
is deposited, through a plasma enhanced ALD process, at a temperature
between about 50° C. and about 200° C., preferably between
about 50° C. and about 150° C.; [0022]a second precursor is
introduced into the reactor, wherein the second precursor is one of Ag,
Au, Cu, Ru, Mg, Ca, Zn, B, Al, In, lanthanides (including Sc, Y, La and
rare earths), Si, Ge, Sn, Ti, Zr, Hf, V, Nb, and Ta; and preferably one
of Ag, Au, Cu, Ru and Ta; [0023]at least one inert fluid (e.g. N2, Ar,
He, etc) and a reaction fluid are provided, the reaction fluid being
either hydrogen or a reducing fluid; [0024]the metal containing precursor
is reacted with the reaction fluid;

[0025]1the reaction fluid is one of H2, H2O, H2O2,
N2, NH3, hydrazine and its alkyl or aryl derivatives,
diethylsilane, trisilylamine, silane, disilane, phenylsilane, a molecule
containing Si--H bonds, dimethylaluminum hydride, hydrogen-containing
radicals such as H., OH., N., NH., NH2., CO, Si2Cl6, and
mixtures thereof; [0026]the pressure in the reactor is between about 1
Pa and about 100,000 Pa; and preferably between about 25 Pa and about
1000 Pa; [0027]metal containing precursor, the inert fluid, and the
reaction fluid are either introduced at least partially simultaneously as
in a chemical vapor deposition process, or are introduced at least
partially sequentially as in an atomic layer deposition process;
[0028]the metal containing precursor has a melting point less than about
50 C; preferably less than about 35° C.; and [0029]the metal
containing precursor is a liquid at room temperature.

[0030]The foregoing has outlined rather broadly the features and technical
advantages of the present invention in order that the detailed
description of the invention that follows may be better understood.
Additional features and advantages of the invention will be described
hereinafter that form the subject of the claims of the invention. It
should be appreciated by those skilled in the art that the conception and
the specific embodiments disclosed may be readily utilized as a basis for
modifying or designing other structures for carrying out the same
purposes of the present invention. It should also be realized by those
skilled in the art that such equivalent constructions do not depart from
the spirit and scope of the invention as set forth in the appended
claims.

Notation and Nomenclature

[0031]Certain terms are used throughout the following description and
claims to refer to particular system components. This document does not
intend to distinguish between components that differ in name but not
function.

[0033]As used herein, the abbreviation, "Me," refers to a methyl group;
the abbreviation, "Et," refers to an ethyl group; the abbreviation, "Pr,"
refers to a propyl group; the abbreviation, "iPr," refers to an isopropyl
group; the abbreviation "acac" refers to acetylacetonato; the
abbreviation "tmhd" refers to 2,2,6,6-tetramethyl-3,5-heptadionato; the
abbreviation "od" refers to 2,4-octadionato; the abbreviation "mhd"
refers to 2-methyl-3,5-hexadinonato; and the abbreviation "tmshd" refers
to 2,2,6,6-tetramethyl-2-sila-heptadionato.

DESCRIPTION OF PREFERRED EMBODIMENTS

[0034]In an embodiment, a precursor compound comprises a precursor with
the general formula:

##STR00004##

[0035]M is one of copper, silver or gold. R, R', and R'' are selected from
hydrogen, a C1-C6 linear, branched or cyclic alkyl group, NO2,
SiR1R2R3; and GeR1R2R3. R1, R2,
R3 are independently selected from hydrogen, and a C1-C6 linear,
branched or cyclic alkyl group. L is a neutral ligand derivated from
ethylene or acetylene.

[0039]The disclosed precursor compounds may be deposited using any
deposition methods known to those of skill in the art. Examples of
suitable deposition methods include without limitation, conventional CVD,
low pressure chemical vapor deposition (LPCVD), atomic layer deposition
(ALD), pulsed chemical vapor deposition (P-CVD), plasma enhanced atomic
layer deposition (PE-ALD), or combinations thereof. In an embodiment, a
first precursor (i.e. the metal containing precursor) may be introduced
into a reaction chamber. The reaction chamber may be any enclosure or
chamber within a device in which deposition methods take place such as
without limitation, a cold-wall type reactor, a hot-wall type reactor, a
single-wafer reactor, a multi-wafer reactor, or other types of deposition
systems under conditions suitable to cause the precursors to react and
form the layers. The first precursor may be introduced into the reaction
chamber by bubbling an inert gas (e.g. N2, He, Ar, etc.) into the
precursor and providing the inert gas plus precursor mixture to the
reactor.

[0040]Generally, the reaction chamber contains one or more substrates on
to which the metal layers or films will be deposited. The one or more
substrates may be any suitable substrate used in semiconductor
manufacturing. Examples of suitable substrates include without
limitation, silicon substrates, silica substrates, silicon nitride
substrates, silicon oxy nitride substrates, tungsten substrates, or
combinations thereof. Additionally, substrates comprising tungsten or
noble metals (e.g. platinum, palladium, rhodium or gold) may be used.

[0041]In an embodiment, a method of depositing a metal film on substrate
may further comprise introducing a second precursor into the reaction
chamber. The second precursor may be a metal precursor containing one or
more metals other than a Group 11 metal. For example, the second
precursor may include without limitation, Mg, Ca, Zn, B, Al, In, Si, Ge,
Sn, Ti, Zr, Hf, V, Nb, Ta, or combinations thereof. Other examples of
metals include rare earth metals and lanthanides. The second precursor
may contain silicon and/or germanium. In particular, examples of suitable
second metal precursors include without limitation, trisilylamine,
silane, disilane, trisilane, bis(tertiary-butylamino)silane (BTBAS),
bis(diethylamino)silane (BDEAS), or combinations thereof. In addition,
the second metal precursor may be an aminosilane having the formula:
SiHx(NR1R2)4-x. The subscript, x, is an integer
between 0 and 4. R1 and R2 may each independently be a hydrogen
group or a C1-C6 alkyl group, either linear, branched, or cyclic. R1
and R2 may be the same or different from on another. In one
embodiment, the second metal precursor is tris(diethylamino)silane
(TriDMAS).

[0042]In an alternative embodiment, the second precursor may be an
aluminum source. Examples of suitable aluminum sources include without
limitation, trimethylaluminum, dimethylaluminum hydride, or combinations
thereof. Additionally, the aluminum source may be an amidoalane having
the formula: AlR1x(NR2R3)3-x. The subscript, x,
is an integer from 0 and 3. R1, R2, and R3 may each
independently be a hydrogen group or a C1-C6 carbon chain, either linear,
branched or cyclic and may each be the same or different from on another.

[0043]In another embodiment, the second precursor may be a tantalum and/or
niobium source selected from the group comprising MCl5 and
corresponding adducts, M(NMe2)5, M(NEt2)4,
M(NEt2)5, or combinations thereof. M represents either tantalum
or niobium. Furthermore, the tantalum and/or niobium source may be an
amino-containing tantalum and/or niobium source having the formula:
M(=NR1)(NR2R3)3. R1, R2, and R3 may
each independently be a hydrogen group or a C1-C6 alkyl group, either
linear, branched, or cyclic. Generally, the weight ratio of the first
metal precursor to the second precursor introduced into the reaction
chamber may range from about 100:1 to about 1:100, alternatively from
about 50:1 to about 1:50, alternatively from about 1:1 to about 10:1.

[0044]In embodiments, the reaction chamber may be maintained at a pressure
ranging from about 1 Pa to about 100,000 Pa, alternatively from about 10
Pa to about 10,000 Pa, alternatively from about 25 Pa to about 1000 Pa.
In addition, the temperature within the reaction chamber may range from
about 70° C. to about 450° C., alternatively from about
70° C. to about 200° C. In some embodiments, the first
precursor has a melting point below about 50° C., preferably below
about 35° C. In some embodiments, the first precursor is a liquid
at room temperature.

[0045]Furthermore, the deposition of the metal film may take place in the
presence of a hydrogen source. Thus, a hydrogen source may be introduced
into the reaction chamber. The hydrogen source may be a fluid or a gas.
Examples of suitable hydrogen sources include without limitation,
H2, H2O, H2O2, N2, NH3, hydrazine and its
alkyl or aryl derivatives, diethylsilane, trisilylamine, silane,
disilane, phenylsilane and any molecule containing Si--H bonds,
dimethylaluminum hydride, hydrogen-containing radicals such as H., OH.,
N., NH., NH2., or combinations thereof. In further embodiments, an
inert gas may be introduced into the reaction chamber. Examples of inert
gases include without limitation, He, Ar, Ne, or combinations thereof. A
reducing fluid may also be introduced in to the reaction chamber.
Examples of suitable reducing fluids include without limitation, carbon
monoxide, Si2Cl6, or combinations thereof.

[0046]The metal precursor and the reaction gas may be introduced
sequentially (as in ALD) or simultaneously (as in CVD) into the reaction
chamber. In one embodiment, the first and second precursors, or the first
precursor and the reaction gas, may be pulsed sequentially or
simultaneously (e.g. pulsed CVD) into the reaction chamber. Each pulse of
the second and/or first metal precursor and may last for a time period
ranging from about 0.01 s to about 10 s, alternatively from about 0.3 s
to about 3 s, alternatively from about 0.5 s to about 2 s. In another
embodiment, the reaction gas, and/or the inert gas may also be pulsed
into the reaction chamber. In such embodiments, the pulse of each gas may
last for a time period ranging from about 0.01 s to about 10 s,
alternatively from about 0.3 s to about 3 s, alternatively from about 0.5
s to about 2 s.

EXAMPLES

[0047]The following non-limiting examples are provided to further
illustrate embodiments of the invention. However, the examples are not
intended to be all inclusive and are not intended to limit the scope of
the inventions described herein. The following examples illustrate
possible deposition methods, according to embodiments of the current
invention.

Example I

Deposition of Copper Metal in CVD Conditions

[0048]In some embodiments, to make the deposition of a copper film on the
surface of a wafer or in a deep trench, one need to vaporize the copper
source according to an embodiment of the current invention, and provide
it into a reactor in which at least one substrate was introduced,
possibly inject an hydrogen source, preferably hydrogen, moisture or
ammonia into said reactor, react or self-decompose the molecules at
appropriate temperature (preferably between 200° C. and
450° C.) and pressure (preferably between 25 Pa and 1000 Pa) for
the duration necessary to achieve either a thin film deposition on the
substrate or to fill out trenches.

Example II

Deposition of Copper Metal in ALD Conditions

[0049]In some embodiments, to make the deposition of a copper film on the
surface of a wafer or in a deep trench, one need to vaporize a copper
source according to an embodiment of the current invention, and provide
it into a reactor in which at least one substrate was introduced, inject
an hydrogen source, preferably hydrogen, moisture or ammonia into said
reactor which contains at least one wafer, react the molecules at
appropriate temperature (preferably between 110° C. and
200° C.) and pressure (preferably between 25 Pa and 1000 Pa) for
the duration necessary to achieve either a thin film deposition on the
substrate or to fill out trenches. More specifically, a cycle is started
when a Cu source is introduced for the pulse time duration, then the Cu
source is purged out of the reactor to remove the Cu molecules which were
not chemisorbed. The hydrogen source is then introduced to reduce the Cu
molecules adsorbed on the wafer surface, hence forming a Cu layer. The
hydrogen source is then purged to complete the cycle. The number of
cycles is set to obtain the desired thickness of copper film.

Example III

Deposition of Copper Metal in Pulsed CVD Conditions

[0050]In some embodiments, to make the deposition of such film on the
surface of a wafer or in a deep trench, one need to vaporize a copper
source according to an embodiment of the current invention, and provide
it into a reactor in which at least one substrate was introduced, inject
an hydrogen source, preferably hydrogen, moisture or ammonia into said
reactor which contains at least one wafer, react the molecules at
appropriate temperature (preferably between 110° C. and
250° C.) and pressure (preferably between 25 Pa and 1000 Pa) for
the duration necessary to achieve either a thin film deposition on the
substrate or to fill out trenches. More specifically, a Cu source is
introduced for the pulse time duration. The hydrogen source is
continuously introduced to reduce the Cu molecules, hence forming a Cu
layer. The number of cycles is set to obtain the desired thickness of
copper film.

Example IV

Deposition of Copper Metal in PEALD Conditions

[0051]In some embodiments, to make the deposition of such film on the
surface of a substrate or in a deep trench, one need to vaporize a copper
source according to an embodiment of the current invention, and provide
it into a reactor in which at least one substrate was introduced, inject
an hydrogen source, preferably hydrogen, moisture or ammonia into said
reactor which contains at least one wafer, react the molecules at
appropriate temperature (preferably between 50° C. and 150°
C.) and pressure (preferably between 25 Pa and 1000 Pa) for the duration
necessary to achieve either a thin film deposition on the substrate or to
fill out trenches. More specifically, a Cu source is introduced for the
pulse time duration. The hydrogen source is continuously introduced but
in these process conditions, the hydrogen source has insufficient
reactivity to reduce the Cu molecules. A plasma is therefore switched on
to activate the hydrogen source making it very reactive, and enable to
reduce the Cu molecules chemisorbed on the surface. When the plasma is
switched off, the cycle is completed as the activated hydrogen source has
a very short lifetime. This allows a shorter lifetime and then a higher
throughput in manufacturing conditions. A layer of Cu is formed. The
number of cycles is set to obtain the desired thickness of copper film.

Example V

Deposition of Copper Films

[0052]In some embodiments, all the information given in Examples I-IV is
applicable in this Example V. The invention is directed to the deposition
of metallic copper films onto a support such as a wafer, in a reactor
using ALD, PEALD, CVD, MOCVD, pulse CVD processes.

Example VI

Deposition of Copper Alloy Film

[0053]All the information given in Example I-IV is applicable in this
Example VI, except that a second M metal source is additionally provided.
A second M containing precursor may also introduced into the reactor
along with the M source of metal. This M containing precursor source is
preferably selected from: [0054]a) a silicon (or germanium) source and is
selected from, but not limited to, the group consisting of trisilylamine,
silane, disilane, trisilane, an aminosilane
SiHx(NR1R2)4-x (where x is comprised between 0 and 4;
R1 and R2 are independently H or a C1-C6 carbon chain, either
linear, branched or cyclic; preferably TriDMAS SiH(NMe2)3;
BTBAS SiH2(NHtBu)2); BDEAS SiH2(NEt2)2) and
mixtures thereof (or their germanium equivalent); or [0055]b) an aluminum
source selected from the group comprising trimethylaluminum,
dimethylaluminum hydride, an amidoalane AlRix(NR'R'')3-x
(where x is comprised between 0 and 4; R1 and R2 are
independently H or a C1-C6 carbon chain, either linear, branched or
cyclic) and mixtures thereof; or [0056]c) a tantalum (or niobium) source
selected from the group comprising TaCl5 and corresponding adducts,
Ta(NMe2)5, Ta(NEt2)4, Ta(NEt2)5,
Ta(=NR1)(NR2R3)3 (each R1 and R2 are
independently H or a C1-C6 carbon chain, either linear, branched or
cyclic and where the amino ligand can have different substituent) and
mixtures thereof; or their niobium counterparts.

[0057]While embodiments of this invention have been shown and described,
modifications thereof can be made by one skilled in the art without
departing from the spirit or teaching of this invention. The embodiments
described herein are exemplary only and not limiting. Many variations and
modifications of the composition and method are possible and within the
scope of the invention. Accordingly the scope of protection is not
limited to the embodiments described herein, but is only limited by the
claims which follow, the scope of which shall include all equivalents of
the subject matter of the claims.